For the first time to our knowledge, the laser performance of Yb3+, Na+-codoped CaF2 single crystals was demonstrated. Self-Q-switched laser operation at 1050nm was observed for 976 nm diode pumping at room temperature. On 5 W of incident power, the repetition rate and width of the self-Q-switched pulses reached 28 kHz and 1.5 micros, respectively. A maximal slope efficiency of 20.3% and minimal threshold absorbed pump power of 30 mW were respectively achieved with different output couplers, showing the promising application of Yb3+, Na+-codoped CaF2 crystals as compact and efficient solid-state lasers.